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1.
Summary Iron(III) complexes of a quadridentate N2S2 donor ligand, 1,2-di(o-aminophenylthio)ethane (DAPTE) and its Schiff Base with salicylaldehyde, a hexadentate N2S2O2 donor ligand,viz. 1,2-di(o-salicylaldiminophenylthio)ethane (H2DSALPTE) have been synthesised and characterised.The Schiff base ligand (1 mol) gave a dark green tri-iron(III) [Fe3(DSALPTE)(HDSALPTE)Cl3]Cl2 complex when reacted with anhydrous iron(III) chloride (1 mol). The Mössbauer data of this complex suggest the presence of three iron sites, one of which is octahedral and the other two tetrahedral. On the other hand, Fe(ClO4)3 reacted smoothly with H2DSALPTE in ethanol to give a mononuclear pseudo-octahedral complex in which the ligand functions in a dibasic hexadentate fashion. Mössbauer data suggest the presence of a low-spin-high-spin equilibrium in the solid state. The manganese(III) and cobalt(III) complexes of the Schiff base, H2DSALPTE, are also studied for the sake of comparison with the corresponding iron(III) complex. The N2S2 ligand, however, formed a low-spin pseudo-octahedral iron(III) complex. The complexes have been characterised by elemental analysis, molar conductance values, cryomagnetic data and i.r., electronic and Mössbauer spectral data.  相似文献   

2.
Summary Two new Schiff bases, N-4-hydroxysalicylidene-glycylglycine (K·GGRS·H2O), N-O-vanillal-glycylglycine (K· GGVS·3H2O) and their manganese(II), cobalt(II), nickel(II) and copper(II) complexes have been synthesized and characterized by elemental analysis, t.g.a., molar conductance, i.r. and u.v. spectral studies. The 13Cn.m.r. spectrum of one of the Schiff base ligands has been recorded. The results show that the ligand is coordinated to the central metal ion via amide nitrogen, imino nitrogen, phenolic oxygen and carboxyl oxygen to form a quadridentate complexes. Some of the complexes exhibit strong inhibitory action towards Candida albicans and Cryptococcus neoformans.  相似文献   

3.
A new macrocyclic ligand, 1,3,5-triaza-2,4:7,8:15,16-tribenzo-9,15-dioxacycloheptadeca-1,5-diene (L) was synthesized by reaction of 2,6-diaminopyridine with 1,4-bis(2-carboxyaldehydephenoxy)butane. Then, its CuII, NiII, PbII, CoIII and LaIII complexes were synthesized by the template effect by reaction of 2,6-diaminopyridine and 1,4-bis (2-carboxyaldehydephenoxy)butane and Cu(NO3)2 · 3H2O, Ni(NO3)2 · 6H2O, Pb(NO3)2, Co(NO3)2 · 6H2O, La (NO3)3 · 6H2O, respectively. The ligand and its metal complexes were characterized by elemental analysis, IR, 1H- and 13C-n.m.r., UV-vis spectra, magnetic susceptibility, thermal gravimetric analysis, conductivity measurements and mass spectra. All complexes are diamagnetic and the CuII complex is binuclear. The CoII complex was oxidised to CoIII.  相似文献   

4.
Summary Ni(NO3)2·6H2O reacts with 2,4-pentanedione S-methylisothiosemicarbazonehydrogen iodide (H2L·HI) in aqueous solution; addition of ammonia then yields [NiL(NH3)]·2H2O, the crystal structure of which has been determined. In the square-planar [NiL(NH3)]·2H2O complex, the ligand, 2,4-pentanedione S-methylisothio-semicarbazone occupies three coordination sites with the bonds to the central atoms involving the terminal nitrogen atoms of the isothiosemicarbazide fragment [Ni–N(3) 1.831 Å and Ni–N(2) 1.842 Å] and the oxygen of the 2,4-pentanedione moiety [Ni–O 1.844 Å]. The template reaction of [NiL(NH3)]·2H2O with 2,4-pentanedione and triethyl orthoformate, HC(OEt)3, gave, by heating the complexes, NiL1 (1) (L1 = dianion of the quadridentate NNNN macrocyclic ligand 2,10-bis(methylthio)-5,7,12,14-tetramethyl-1,3,4,8,9,11 -hexaazacyclotetradeca-2,4,6,9,12,-14-hexaene) and NiL2 (2) (L2 = dianion of the quadridentate ONNO ligand 3-acetyl-6-thiomethyl-9-methyl-5,7,8-tri-azadodeca-3,6,9-triene-2,11-dione) presents described.  相似文献   

5.
Vicinal carbonyl oxime (HL1) and oxime-imine (H2L2) ligands and their mononuclear Ru(III) and Cu(II), heterodinuclear Ru(III)-Mn(II), Ru(III)-Ni(II), Ru(III)-Cu(II), and heterotrinuclear Ru(III)-Cu(II)-Ru(III) chelates were synthesized and characterized by elemental analysis, molar conductivity, IR, ESR, ICP-OES, magnetic moment measurements, and thermal analyses studies. The free ligands were also characterized by 1H NMR spectra. The carbonyl-oxime ligand coordinates through the oxygen of =N-OH to form a six-membered chelate ring. The quadridentate tetraaza ligand (H2L2) obtained by condensing of the bidentate ligand 1-p-diphenylmethane-2-hydroxyimino-2-(1-naphthylamino)-1-ethanone (HL1) with 1,2-phenylenediamine coordinates with Ru(III) through its nitrogen donors in the equatorial position with the loss of one of the oxime protons and concomitant formation of an intramolecular hydrogen bond. Stoichiometric and spectral results of the metal complexes indicated that the metal: ligand ratios in the mononuclear complexes of the ligand (HL1) were found to be 1: 2, while these ratios were 1: 1 in the mononuclear complexes of the ligand (H2L2). The metal: ligand ratios of the dinuclear complexes were found to be 2: 1, and this ratio was 3: 2 in the trinuclear complex. The article is published in the original.  相似文献   

6.
Cobalt(II) and copper(II) complexes with three dioxime ligands cyclohexylamine-p-tolylglyoxime (L1H2), tert-butyl amine-p-tolylglioxime (L2H2) and sec-butylamine-p-tolylglyoxime (L3H2), have been prepared. The metal to ligand ratios of the complexes were found to be 1?:?2. The Cu(II) complexes of these ligands are proposed to be square planar; the Co(II) complexes are proposed to be octahedral with water molecules as axial ligands. Ligands and complexes are soluble in common solvents such as DMSO, DMF, CHCl3 and C2H5OH. The ligands have been characterized by elemental analysis, IR, UV-VIS, 1H?NMR, 13C?NMR and thermogravimetric analysis (TGA). The complexes were characterized by elemental analysis, IR, UV-VIS, magnetic susceptibility measurements, thermogravimetric analysis (TGA) and electrochemistry. Electrochemical properties of metal complexes show quasi-reversible one-electron redox processes. However, Co(L1H)2 and Cu(L1H)2 complexes show another oxidation peak in the positive region. This single irreversible oxidation peak is caused by the cyclic ring of the ligand. Data also revealed that the electron transfer rates of metal complexes with L1H2 are higher than the other complexes.  相似文献   

7.
N′-(4′-Benzo[15-crown-5]naphthylaminoglyoxime (H2L) and its sodium chloride complex (H2L·NaCl) have been prepared from 2-naphthylchloroglyoxime, 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II) and copper(II) complexes of H2L and H2L·NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF2+-capped Ni(II), Co(III) and mononuclear complexes of thevic-dioxime were prepared. The macrocyclic ligands and their transition metal complexes have been characterized on the basis of IR, 1H NMR spectroscopy and elemental analyses data.  相似文献   

8.
4-(Chloroacetyl)diphenyl ether was synthesized from chloroacetyl chloride and diphenyl ether in the presence of AlCl3 as catalyst in a Friedel-Crafts reaction. Then, its keto oxime and dioxime derivatives were prepared. 4-phenoxy-(N-4-chlorophenylamino)phenylglyoxime (H2L) was synthesized from 4-(phenoxy)chlorophenylglyoxime and 4-chloroaniline. Ni(II), Co(II) and Cu(II) complexes of H2L were obtained. The mononuclear Ni(II), Co(II) and Cu(II) complexes of H2L have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The structure of the ligand was identified by FT-IR, 1H NMR, 13C NMR, 13C NMR (APT) spectroscopy and elemental analysis data. The structures of the complexes were characterized on the basis of FT-IR, ICP-AES, UV-Vis, elemental analysis, magnetic susceptibility measurements, and cyclic voltammetry. The electrochemical measurements were obtained by using cyclic voltammetry in DMF solution at room temperature. The electrochemical behaviors of H2L and its complexes showed that the redox process of H2L has one irreversible oxidation wave, whereas the redox processes of the complexes have both oxidation and reduction waves with metal centered.  相似文献   

9.
pH potentiometric and spectrophotometric investigations on the complex formation equilibria of CuII with iminodiacetate (ida2−) and heterocyclic N-bases, viz. imidazole and benzimidazole (B), in aqueous solution in binary and ternary systems using different molar ratios of the reactants indicated the formation of complexes of the types, Cu(ida), Cu(ida)(OH), (ida)Cu(OH)Cu(ida), Cu(B)2+, Cu(H-1B)+, Cu(ida)(H−1B), (ida)Cu(B)Cu(ida) and (ida)Cu(H−1B)Cu(ida). Formation constants of the complexes at 25 ±1° at a fixed ionic strength,I = 0.1 mol dm−3 (NaNO3) in aqueous solution were evaluated and the complex formation equilibria were elucidated with the aid of speciation curves. Departure of the experimental values of the reproportionation constants(ΔlogK cu) of ternary Cu(ida)(H−1B) complexes from the statistically expected values, despite their formation in appreciable amounts at equilibrium, were assigned tofac(f)-mer(m) equilibria of the ida2− ligand coordinated to CuII, as the N-heterocyclic donors, (H−1B), coordinatetrans- to the N-(ida2−) atom in the binary Cu(ida) f complex to form the ternary Cu(ida) m (H−1B) complexes  相似文献   

10.
A new series of Cu(II), Ni(II), and Co(II) complexes have been synthesized from 3-formylchromoniminopropylsilatrane (C19H24O5N2Si) (2) and 3-formylchromoniminopropyltriethoxysilane (1). Silatrane ligand (C19H24O5N2Si) (2) has been synthesized by the reaction between 3-aminopropyltriethoxysilane and 3-formylchromone followed by a treatment with triethanolamine. The nature of bonding and the geometry of the complexes have been deduced from elemental analyses, magnetic susceptibility, infrared, electronic, 1H NMR, 13C NMR, and ESR spectral studies. The electronic absorption spectra and magnetic susceptibility measurements of the complexes indicate square planar geometry for Cu(II) and Ni(II) and tetrahedral geometry for Co(II). The redox behavior of copper complexes was studied by cyclic voltammetry. The biological activity of the ligand and metal complexes has been studied on Klebsiella pneumoniae, Staphylococcus aureus, Escherichia Coli, and Bacillus subtilis by the well diffusion method using acetonitrile as solvent. The zone of inhibition values were measured at 37°C for 24 h. Antimicrobial screening tests show better results for the metal complexes than the ligand.  相似文献   

11.
Sodium4-hydroxy-3-([2-picolinoylhydrazineylidene]methyl)benzenesulfonate (NaH2PH) was synthesized as a novel water-soluble ligand, by the condensation of picolinohydrazide with sodium 3-formyl-4-hydroxybenzenesulfonate. The (NaH2PH) ligand and its isolated Co (II), Fe (III), Hg (II), and Pd (II) complexes were analyzed by elemental analysis and characterized by spectroscopic (Fourier transform infrared spectroscopy, UV–visible, powder XRD, 1H NMR,13C NMR, MS) and magnetic measurements. By comparing IR spectra of both ligand and the metal complexes, one can assume that the (NaH2PH) ligand behaves as a bi-negative tetradentate (ONNO) in [Co (NaPH)(H2O)2].3H2O, and a mono-negative tridentate (ONO) in [Fe (NaPH)Cl2(H2O)] complex, whereas in [Hg2(NaPH)Cl2(H2O)] complex, (NaH2PH) coordinates as a bi-negative pentadentate (ONNNO) ligand via deprotonated OH group of phenolic ring (C=N)Py and (C=N*) coordinated to one of Hg (II) ion and the oxygen atom of enolic group and (C=N)az group with the another Hg (II) ion. Moreover, (NaH2PH) acts as bi-negative tridentate (ONO) ligand in [Pd (NaPH)(H2O)].2H2O complex. The geometries of complexes were suggested based on the UV–visible spectra, magnetic measurements and confirmed by applying discrete Fourier transform (DFT) optimization studies. The thermal fragmentation of both [Pd (NaPH)(H2O)].2H2O and [Co (NaPH)(H2O)2].3H2O complexes was performed, and the kinetic and thermodynamic parameters were computed using the Coats–Redfern and Horowitz–Metzger methods. The redox behavior of divalent ions of cobalt and mercury were discussed by the cyclic voltammetry technique in the presence and absence of (NaH2PH) ligand. Biological potencies of the ligand and its metal complexes were evaluated as antioxidants (ABTS and DPPH), anticancer, DNA, and antimicrobial (Staphylococcus aureus and Bacillus subtilis as Gram (+) bacteria, Escherichia coli and Pseudomonas aeruginosa as Gram (−) bacteria, and Candida albicans as fungi).  相似文献   

12.
A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H2Pymdo) (3) has been synthesized in H2O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H2Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H2Pymdo) and its copper(II) complexes were characterized by 1H-n.m.r., 13C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H2Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H2Pymdo and its Cu(II) complexes.  相似文献   

13.
o-Hydroxyacetophenone (N-benzoyl)glycyl hydrazone (o-HABzGH) forms complexes of the types [M(o-HABzGH)Cl2(H2O)2]Cl and [M(o-HABzGH-2H)OH(H2O)2], where M = Y(III), Gd(III), Tb(III) and Dy(III). The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility, infrared, electronic,1H NMR and13C NMR spectral techniques. The nephelauxetic ratio (β), covalency (δ), bonding parameter (b 1/2) and angular overlap parameter (η) have been calculated from Dy(III) complexes. Infrared and NMR spectral studies show thato-HABzGH acts as a neutral bidentate ligand in the adduct complexes and as a dinegative tridentate one in the neutral complexes. A coordination number of six has been proposed for the metal ion in all the complexes.  相似文献   

14.
Novel monobasic tridentate ONS donor ligand (HL) was synthesized from the condensation reaction of chromone-3-carboxaldehyde with S-benzyldithiocarbazate (SBDTC). Reaction of the ligand with the metal ions copper(II), nickel(II), cobalt(II), oxidovanadium(IV), cerium(III), manganese(II), zinc(II), and cadmium(II) afforded dimeric complexes with the general formula [ML(Y)m(H2O)x]2·(Y)m·nH2zCH3OH, Y?=?NO3 or Cl, m?=?0–2, x?=?0–2, n?=?0–2, and z?=?0–1 for all complexes except oxidovanadium(IV) complex which has the formula [VOL(H2O)]2(SO4). Structures of the ligand and its metal complexes were established through elemental, spectroscopic data (FT-IR, UV-Vis, and mass), thermal analyses, as well as conductivity and magnetic susceptibility measurements. The geometrical structures of the metal complexes are octahedral and square planar. The ligand and its complexes were subjected to in vitro bioassays against the gram-negative and gram-positive bacteria and the fungus strain with good results for some of these compounds. The antitumor activity of the ligand and its copper(II) and oxidovanadium(IV) complexes were investigated against HepG2 cell line. The molecular parameters of the ligand and its metal complexes have been calculated on the basis of DFT level implemented in the Gaussian 09 program, and computed data were correlated with the experimental results. The HOMO→LUMO electron transition potentially occurs from S-benzyldithiocarbazate to chromone moieties with 4.048?eV. The Mn(II) complex has the highest value of energy barrier, while Cu(II) complex has the lowest value among the complexes. All synthesized complexes have energy gap lower than free ligand and therefore these complexes are more reactive than the free ligand.  相似文献   

15.
水热条件下,合成了2个三维配位聚合物{[Zn4(L)2(o-bix)2]·2H2O}n(1),{[Co4(L)2(o-bix)2]·2H2O}n(2)(H4L=5,5′-亚甲基二间苯二甲酸,o-bix=1,2-双(咪唑基-1-甲基)苯),并通过红外、热重和X-射线单晶衍射进行了表征。X-射线衍射结果表明这2个化合物具有相似的结构。在1个不对称单元中,化合物包含2个不同配位环境的金属离子,1个L4-配体,1个o-bix分子以及1个游离的溶剂水分子。中心金属离子分别采用畸变的四面体和四方锥构型,形成两类双核单元,然后通过全部脱质子的L4-形成3D孔洞结构,o-bix配体通过连接两类双核金属原子填充于孔洞之中,形成3D紧密堆积结构。对化合物的红外和热重性质进行了表征。  相似文献   

16.
利用8-羟基喹啉原位反应,通过溶剂热方法制备出3种新颖的d~(10)配合物[M_2(HL)_3]NO_3·H_2O (M=Cd (1),Zn (2,3)),H_2L为1,1-(7,7′-二-(8-羟基喹啉))。单晶结构表明,3种配合物有着相同的带正电荷的结构单元[M_2(HL)_3]~+,但由于客体分子所处空间位置的不同表现为不同的空间结构,配合物1和3结晶于六方晶系(P6_3/m),配合物2结晶于三方晶系(R3)。中心金属离子以六配位的模式与来自HL-配体上的3个氧原子和3个氮原子形成一个轻微扭曲的八面体几何构型。存在于HL-配体与客体分子(NO_3~-,H_2O)间大量的弱作用力在结构空间堆积上起到了重要的作用。3种配合物均具有良好的热稳定性和绿色荧光发射性质。同时,通过从配合物1中提取出原位生成的配体H_2L,首次报道了其蓝色荧光发射性质。  相似文献   

17.
The Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II) and Cd (II) complexes were prepared by reaction of its metal chlorides with new azo-dye ligand (H2L). The ligand derived from 4,4′-oxydianiline and 2-amino-4-chlorophenol was synthesized in a 1:2 molar ratio. The structure of the ligand and its metal complexes was investigated using different tools such as elemental analysis (C, H, N and M), molar conductivity, IR, UV–vis, 1H-NMR, mass spectrometry and thermogravimetric and differential thermogravimetric studies. The data showed that the ligand acted as a N,N,O,O-binegative tetradentate ligand. All metal complexes had a octahedral structure as depicted by spectral and elemental analyses. The conductivity data showed the electrolytic nature of the Cr (III) and Fe (III) complexes while the other complexes were nonelectrolytes. Thermal analysis studies showed the decomposition of the complexes in four to five steps with the weight loss of hydrated water in the first decomposition step followed by the coordinated water and ligand molecules. Biological activity was tested for the prepared compounds against four bacterial species (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa) and against two fungal species (Aspergillus fumigatus and Candida albicans). Also, all complexes were screened for anticancer activities against a breast cancer (MCF-7) cell line. The [Co(L)(H2O)2] complex showed the lowest IC50 value. Molecular docking is a key tool in computer drug design. Therefore, investigation of protein receptors and ligand interaction plays a vital role in the design of structurally based drugs. As a result, docking studies were investigated for H2L ligand, [Mn(L)(H2O)2] and [Ni(L)(H2O)2] complexes with 5KBC, 3V7B and 4G9M receptors.  相似文献   

18.
A new unsymmetrical Schiff base ligand (H2LLi) was synthesized using L-lysine, salicylaldehyde, and 2-hydroxy-1-naphthaldehyde. Three rare-earth ion complexes of this ligand, [REE(H2L)(NO3)]NO3 · 2H2O (REE = La, Sm, Ho), have been prepared and characterized by elemental analyses, IR spectra, UV spectra, TG-DTG, and molar conductance. The antibacterial activity of the ligand and its complexes are also studied. The antibacterial experiments indicate that this ligand and its complexes possess antibacterial activity against Escherichia coli, Staphylococcus aureus and Bacillus subtilis and the complexes have higher activity than that of the ligand. The article was submitted by the authors in English.  相似文献   

19.
N,N′-bis(salicylidene)-1,3-propanediamine (LH2), N,N′-bis(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH2), N,N′-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH3), N,N′-bis(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH2) and N,N′-bis(2-hydroxyacetophenone)-2,2′-dimethyl-1,3-propanediamine (LACDMH2) were synthesized and reduced to their phenol-amine form in alcoholic media using NaBH4 (LHH2, LDMHH2, LOHHH2, LACHH2 and LACDMHH2). Heterodinuclear complexes were synthesized using Ni(II), Zn(II) and Cd(II) salts, according to the template method in DMF media. The complex structures were analyzed using elemental analysis, IR spectroscopy, and thermogravimetry. Suitable crystals of only one complex were obtained and its structure determined using X-ray diffraction, NiLACH·CdBr2·DMF2, space group orthorhombic, Pbca, a=20.249, b=14.881, c=20.565 ? and Z=8. The heterodinuclear complexes were seen to be of [Ni·ligand·MX2·DMF2] structure (ligand=LH2−, LDMH2−, LOHH2−, LACH2−, LACDMH2−, M=ZnII, CdII, X=Br, I). Thermogravimetric analysis showed irreversible bond breakage of the coordinatively bonded DMF molecules followed by decomposition at this temperature.  相似文献   

20.
用Demko-Sharpless方法自制的双四唑胺配体,再混以乙二胺和丙二胺螯合配体,合成了2个新颖的铜的配合物Cu(bta)(en)(H2O)(1)与Cu(bta)(1,3-pda)(H2O)(2)。X-射线单晶衍射表征了2个配合物的结构。2个配合物的水溶液都表现出了双四唑胺配体的特征吸收波长与荧光发射波长。  相似文献   

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